Stabilizing polymeric material against the destructive influence of high-energy radiation is the subject of intense research efforts. In recent years, a large number of light stabilizers based on sterically hindered amines has been developed which ensure the stabilization of polymeric material in an outstanding manner. Nevertheless, low molecular mass stabilizers of this class of substance, in particular, suffer from the disadvantage of their ready extractability and high volatility from the polymer material to be stabilized, so that following a certain period of use there is unwanted breakdown of the material. For this reason, a considerable number of polymeric stabilizers based on sterically hindered amines have been prepared, which possess said disadvantages to a lesser degree if at all. By way of example there may be mentioned stabilizers as described, for instance, in EP-A-93693, DE-A-2719131, EP-A-343717 and EP-A-402889. However, there is a constant demand for new, more effective stabilizers which possess improved photoprotective or additional, better performance properties.
EP-A-28318 describes the preparation and polymerization, and EP-A-402889 the improved polymerization, of compounds of the formula 
to form oligomeric and, respectively, polymeric stabilizers, while German Patent Application No. 19608163.7 describes an effective, high-yielding and eco-friendly method of preparing such stabilizers.
European Patent Application 95 109 777.3 and EP-A-57885 (cf. Example 11 therein) describe derivatives of compounds of the formula 
which constitute new and effective light stabilizers.
It has surprisingly now been found that reaction of compounds of the formula (I) with compounds of the formula (II) 
produces new stabilizers of the formula (III).
The invention therefore provides novel compounds of the formula (III) 
in which
n and m independently of one another are a number from 0 to 100, but n and m cannot both be 0,
R1 is hydrogen, C5-C7-cycloalkyl, or a C1-C12-alkyl group,
R2 and R3 independently of one another are a hydrogen atom or a C1-C18-alkyl group or, together with the carbon atom connecting them, are a 5- to 13-membered ring or, together with the carbon atom connecting them, are a group of the formula (IV) 
R4 and R5 independently of one another are either hydrogen or a C1-C22-alkyl group,
an oxygen radical O*, xe2x80x94OH, xe2x80x94NO, xe2x80x94CH2CN, benzyl, allyl, a C1-C30-alkyloxy group, a C5-C12-cycloalkyloxy group, a C6-C10-aryloxy group in which additionally the aryl radical may also be substituted, a C7-C20-arylalkyloxy group in which additionally the aryl radical may also be substituted, a C3-C10-alkenyl group, a C3-C6-alkynyl group, a C1-C10-acyl group, halogen or C7-C9-phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C4-alkyl.
Also highly suitable are compounds of the formula (III) in which
n and m independently of one another are a number from 0 to 10, but n and m cannot both be 0,
R1 is hydrogen, C6-cycloalkyl, or a C1-C4-alkyl group,
R2 and R3 independently of one another are a hydrogen atom or a C1-C8-alkyl group, or, together with the carbon atom connecting them, are a 6- to 12-membered ring or, together with the carbon atom connecting them, are a group of the formula (IV),
R4 and R5 independently of one another are either hydrogen or a C1-C5-alkyl group,
an oxygen radical O*, xe2x80x94OH, xe2x80x94NO, xe2x80x94CH2CN, benzyl, allyl, a C1-C10-alkyloxy group, a C5-C6-cycloalkyloxy group, a C6-C7-aryloxy group in which additionally the aryl radical can also be substituted, a C7-C10-arylalkyloxy group in which additionally the aryl radical can also be substituted, a C3-C6-alkenyl group, a C3-C6-alkynyl group, a C1-C4-acyl group, halogen or C7-C9-phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C2-alkyl.
Particularly preferred compounds of the formula (III) are those in which
n and m independently of one another are a number from 0 to 5, but n and m cannot both be 0,
R1 is methyl,
R2 and R3, together with the carbon atom connecting them, are a 12-membered ring
or, together with the carbon atom connecting them, are a group of the formula (IV),
R4 and R5 independently of one another are hydrogen, methyl, acetyl, octyloxy or cyclohexyloxy.
The invention also relates to a general process for the preparation of compounds of the formula (III), and to their use for stabilizing organic material, and to an organic, preferably polymeric material stabilized with compounds of the formula (III), said material being selected in particular from plastics, coating compositions, lacquers and oils or their precursors.
The preparation of compounds of the formula (III) where R4=hydrogen is carried out by reacting compounds of the formula (I) with compounds of the formula (II). To prepare (III) it is possible to employ processes already known per se, as are described, for example, in C. Ferri, Reaktionen der organischen Synthese, 1978, page 504 or Houben-Weyl, Vol. VI/3, page 456 or Vol. XI/1, page 311. The reaction can be carried out with or without solvents; suitable solvents are preferably high-boiling, aprotic solvents, such as toluene, xylene, mesitylene or decalin, for example. The reaction can be implemented with or without catalyst (especially by thermal means), with suitable catalysts being bases, preferably metal salts, especially alkali metal hydroxides, such as NaOH or KOH, for example. A preferred preparation process is the reaction of (I) and (II) directly in bulk, without using a solvent and without catalyst. In this case (I) and (II) are polymerized in a molar ratio in the range from 1:1 (equimolar) to 100:1 in the temperature range from 100 to 300xc2x0 C., preferably from 120 to 250xc2x0 C. and, in particular, from 160 to 220xc2x0 C., preferably in the absence of oxygen. A solventless polymerization in vacuo is particularly suitable. The product in this case, after working up, is a solid, colorless, amorphous resin. The molecular weight of the resulting oligomer or polymer can be controlled as a function of the temperature, the molar ratio in which the starting materials are employed, and/or the reaction time. Methods for subsequent modification of R4 (R4 other than hydrogen) are sufficiently well known from the prior art; for example, from EP-A-0 705 896 or from EP-A-0 690 060. Of outstanding importance in particular are the derivatives of the compound (III) where R4=H or R4=methyl.
The compounds of the invention are outstandingly suitable for stabilizing organic material against the action of light, oxygen and heat. They can be added to the organic material to be stabilized, prior to, during or after polymerization, in solid form, as a melt, as a solution in solvents or else as a masterbatch. The solutions may comprise the new stabilizer, for example, in 5-80% concentrations; a masterbatch is particularly appropriate if it comprises the new stabilizer in a concentration of from 1 to 80%, but preferably 5-30%, with the remainder of the masterbatch comprising a polymer compatible with the polymer to be stabilized. Both the solution and the masterbatch may additionally include other stabilizers or effect substances, examples being UV absorbers, antioxidants, pigments, acid scavengers or fillers. The new stabilizers are preferably employed such that their concentration in the polymer to be stabilized is from 0.001 to 5% by weight, preferably from 0.02 to 2% by weight, based on the organic material, and they are present either alone or in combination with further additives. The term organic material embraces, for example, precursors for plastics, coating materials, lacquers and oils, but especially the plastics, coating materials, lacquers and oils themselves.
The compounds of the formula (III) are particularly suitable for stabilizing films, fibers, tapes, multifilaments, fabrics, extruded, blow-molded, injection molded and thermoformed articles, powder coating materials, printing inks, toner inks, photographic material, pigments, wood stains, leathers, architectural paints, protective coatings for steel structures, lubricating oils, machine oils, bitumen or asphalt and for stabilizing compounds which have a tendency to undergo spontaneous polymerization.
The compounds of the formula (III) of the invention can also be employed, advantageously, in combinations with further stabilizers. The result of these new combinations are mixtures having an improved profile of properties with respect to the individual components, such as synergy in the photoprotective effect, for example.
Combining the compounds of the formula (III) with monomeric HALS stabilizers in a weight ratio of from 10:1 to 1:10 is particularly advantageous. Combinations of polymeric with monomeric HALS stabilizers are described, for instance, in EP-A-80431 and EP-A-632092. It is particularly advantageous to combine, in accordance with the invention, (III) with compounds of the formulae A1 to A10. 
in which
R1 and R4 are as defined above,
R6 is an aromatic radical substituted one or more times by hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen, cyano, carboxyl, nitro, amino, C1-C4-alkylamino, C1-C4-dialkylamino, or acyl,
o is 1 or 2, 
in which
R1 and R4 are as defined in claim 1,
p=1 or2 and
if p=1,
R7 is C1-C22-alkyl, C2-C18-oxaalkyl, C2-C18-thiaalkyl, C2-C18-azaalkyl or C2-C8-alkenyl;
if p=2,
R7 is C1-C22-alkylene, C2-C18-oxaalkylene, C2-C18-thiaalkylene,
C2-C18-azaalkylene or C2-C8-alkenylene; 
in which
R1 and R4 are as defined in claim 1,
R8 and R9 independently of one another are hydrogen, C1-C6-alkyl, C7-C12-aralkyl, -aryl or carboxylic ester,
R8 and R9 together are a tetra- or pentamethyl group; 
in which
R1, R2, R3 and R4 are as defined in claim 1,
q is a number 1 or 2,
R10 is hydrogen, methyl, phenyl or carb-C1-C21-alkoxy,
R11 is hydrogen or methyl,
R12, if q=1, is hydrogen, C1-C21-alkyl, C2-C22-alkenyl, C5-C12-cycloalkyl, a radical of the formula 
where
R1 and R5 are as defined in claim 1, and
R12, if q=2, is C1-C18-alkylene, C5-C9-cycloalkylene or arylene; 
where R1, R4, R7 and p are as defined above; 
where R1, R4, R7 and p are as defined above; 
where R1, R4 are as defined above,
R30 is hydrogen, C1-C12-alkyl, C5-C12-cycloalkyl, phenyl or C7-C9-phenylalkyl, and
a is a number from 1 to 10; 
where R1 and R4 are as defined above and R7 is as defined for p=1 in the formula A2;
a product A10 obtainable by reacting a polyamine of the formula A10a with formula A10b:
HRNxe2x80x94(CH2)n5xe2x80x2xe2x80x94NHxe2x80x94(CH2)n5xe2x80x2xe2x80x3xe2x80x94NHxe2x80x94(CH2)n5xe2x80x2xe2x80x3xe2x80x94NHRxe2x80x2R and Rxe2x80x2=H, CH3xe2x80x83xe2x80x83(A10a)

where
R1,R4 and R30 are as defined above,
n5xe2x80x2, n5xe2x80x3 and n5xe2x80x2xe2x80x3 independently of one another are a number from 2 to 12.
Preference is given to mixtures of compounds of the formula (III) with compounds of the formulae A1 to A10 in which
n and m independently of one another are a number from 0 to 10, but n and m cannot both be 0,
R1 is hydrogen or a C1-C4-alkyl group,
R2 and R3 independently of one another are a hydrogen atom or a C1-C8-alkyl group or, together with the carbon atom connecting them, are a 6- to 12-membered ring or, together with the carbon atom connecting them, are a group of the formula (IV),
R and R5 independently of one another are either hydrogen or a C1-C5-alkyl group, an oxygen radical O*, xe2x80x94OH, xe2x80x94NO, xe2x80x94CH2CN, benzyl, allyl, a C1-C10-alkyloxy group, a C5-C6-cycloalkyloxy group, a C6-C7-aryloxy group in which additionally the aryl radical may also be substituted; a C7-C10-arylalkyloxy group in which additionally the aryl radical may also be substituted, a C3-C6-alkenyl group, a C3-C6-alkynyl group, a C1-C4-acyl group, halogen or C7-C9-phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C2-alkyl,
R7 is a straight-chain C1-C10-alkylene (if p=2); C1-C12-alkyl (if p=1)
R8 and R9 independently of one another are hydrogen, C1-C2-alkyl, C7-C8-arylalkyl, aryl- or carboxylic ester,
R10 is hydrogen, methyl, phenyl or C1-C2-alkoxy,
R11 is hydrogen or methyl,
R12, if q=1, is hydrogen, C1-C16-alkyl, C2-C16-alkenyl, C5-C6-cycloalkyl, a radical of the formula 
R12, if q=2, is C1-C16-alkylene, C5-C6-cycloalkylene or arylene,
R30 is hydrogen, C1-C8-alkyl, C5-C7-cycloalkyl, phenyl or C7-C8-phenylalkyl,
a is 1 to 5,
o 1 and
p 2 to 5.
Very particular preference is given to mixtures in which
n and m independently of one another are a number 0-5, but n and m cannot both be 0,
R1 is methyl,
R2 and R3, together with the carbon atom connecting them, are a 12-membered ring or, together with the carbon atom connecting them, are a group of the formula (IV),
R4 and R5 independently of one another are hydrogen, methyl, acetyl, octyloxy or cyclohexyloxy,
R6 is p-methoxyphenyl,
R7 is octamethylene, hexamethylene or ethylene (if p=2), dodecyl (if p=1),
R8 and R9 are hydrogen,
R10 is hydrogen,
R11 is hydrogen,
R12 is dodecamethylene or tetradecarnethylene,
R30 is cyclohexyl or n-butyl,
a is 2,
o is 1,
p is 2
and q is 1.
The following compounds are especially suitable in a mixture with compounds of the formula (III): 
A particularly suitable embodiment of the invention comprises mixtures of a compound of the formula (III) with one or more stabilizers based on sterically hindered amines, where the co-component(s) is (are) TINUVIN(copyright) 770, TINUVIN(copyright) 765, TINUVIN(copyright) 123, HOSTAVIN(copyright) N 20, HOSTAVIN(copyright) N 24, UVINUL(copyright) 4049, SANDUVOR(copyright) PR31, UNIVUL(copyright) 4050, GOODRITE(copyright) UV 3034 or GOODRITE(copyright) 3150, SANDUVOR(copyright) 3055, SANDUVOR(copyright) 3056, SANDUVOR(copyright) 3058, CHIMASSORB(copyright) 119 and CHIMASSORB(copyright) 905.
The compound of the formula (III) of the invention can also be employed advantageously with polymeric HALS stabilizers in a weight ratio of from 10:1 to 1:10. The result of these new combinations are mixtures which have an improved profile of properties with respect to the individual components; for example, synergy in the photoprotective effect. Combinations of polymeric HALS stabilizers are described, for example, in EP-A-252877, EP-A-709426, Research Disclosure January 1993 No. 34549, EP-A-723990.
A particularly preferred embodiment in this context comprises the combinations of the compound (III) with polymeric HALS compounds of the formulae B1 to B7: 
in which
R1 is hydrogen, C5-C7-cycloalkyl or a C1-C12-alkyl group,
R13 is hydrogen or methyl,
R14 is a direct bond or C1-C10-alkylene and
r is a number from 2 to 50; 
where
R1 and R4 are as defined for formula (III),
R15 and R18 independently of one another are a direct bond or a group xe2x80x94N(R22)xe2x80x94COxe2x80x94R23xe2x80x94COxe2x80x94N(R24)xe2x80x94,
R22 and R24 independently of one another are hydrogen, C1-C8-alkyl, C5-C12-cyclolalkyl, phenyl, C7-C9-phenylalkyl, or a group of the formula 
R23 is a direct bond or C1-C4-alkylene,
R16, R17, R20, R21 independently of one another are hydrogen, C1-C30-alkyl, C5-C12-cycloalkyl, phenyl, or a group of the formula B2a,
R19 is hydrogen, C1-C30-alkyl, C5-C12-cycloalkyl, C7-C9-phenylalkyl, phenyl or a group of the formula B2a and
s is a number from 1 to 50; 
where
R1, R4 and s are as defined above,
R25, R26, R27, R28 and R29 independently of one another are a direct bond or C1-C10-alkylene;
a product B4 obtainable by reacting a polyamine of the formula B4a with cyanuric chloride and then reacting the resulting product with a compound of the formula B4b, 
where
R1 and R4 are as defined for formula (III),
n5xe2x80x2, n5xe2x80x3 and n5xe2x80x2xe2x80x3independently of one another are a number from 2 to 12,
R30 is as defined above; where B4 is a compound of the formula B4-1, B4-2, B4-3 
or a mixture thereof, in which
n5 is 1 to 20,
R4 and R30 are as defined above; 
where
r is as defined for formula B1,
R31, R33 and R34 independently of one another are hydrogen, C1-C12-alkyl, C5-C12-cycloalkyl, C1-C4-alkyl-substituted C5-C12-cycloalkyl, phenyl, xe2x80x94OHxe2x80x94 and/or C1-C10-alkyl-substituted phenyl, C7-C9-phenylalkyl, C7-C9-phenylalkyl substituted on the phenyl radical by xe2x80x94OH and/or C1-C10-alkyl, or a group of the formula B5a 
where
R1 and R5 are as defined above, and
R32 is C2-C18-alkylene, C5-C7-cycloalkylene or C1-C4-alkylenedi(C5-C7-cycloalkylene) or the radicals R31, R32 and R33 together with the nitrogen atoms to which they are attached, form a 5- to 10-membered heterocyclic ring, and where at least one of the radicals R31, R33 and R34 is a group of the formula B5a; 
in which
R31, R32, R33 and r are as defined above,
R35 and R36 independently of one another can have the definition of R34, or R35 and R36, together with the nitrogen atom to which they are attached, form a 5- to 10-membered heterocyclic ring which may in addition to the nitrogen heteroatom contain one or more other heteroatoms, preferably an oxygen atom, and at least one of the radicals R31, R33, R35 and/or R36 is a group of the formula (B5a); 
where
R1 and R4 are as defined in claim 1,
s is as defined for formula B3,
R37 is C1-C10-alkyl, C5-C12-cycloalkyl, C1-C4-alkyl-substituted C5-C12-cycloalkyl, phenyl or C1-C10-alkyl-substituted phenyl, and
R38 is C3-C10-alkylene.
The compounds described as components B1 to B4 are essentially known (in some cases obtainable commercially) and can be prepared by known methods as described, for example, in U.S. Pat. No. 4,233,412, U.S. Pat. No. 4,340,534, U.S. Pat. No. 4,857,595, DD-A-262 439 (Derwent 89-122 983/17, Chemical Abstracts 111:58 964u), DE-A-4 239 437 (Derwent 94-177 274/22), U.S. Pat. No. 4,529,760, U.S. Pat. No. 4,477,615 and Chemical Abstractsxe2x80x94CAS No. 136 504-96-6.
Component B4 can be prepared in analogy to known methods: for example, by reacting a polyamine of the formula B4a with cyanuric chloride in a molar ratio of from 1:2 to 1:4 in the presence of anhydrous lithium, sodium or potassium carbonate in an organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl alcohol at a temperature of from xe2x88x9220xc2x0 C. to +10xc2x0 C., preferably from xe2x88x9210xc2x0 C. to +10xc2x0 C. and, in particular, from 0xc2x0 C. to +10xc2x0 C. for 2 to 8 hours and then reacting the resulting product with a 2,2,6,6-tetramethyl-4-piperidylamine of the formula B4b. The molar ratio of 2,2,6,6-tetramethyl-4-piperidylamine to polyamine of the formula B4a employed is, for example, from 4:1 to 8:1. The amount of 2,2,6,6-tetramethyl-4-piperidylamine can be added all at once or in two or more portions with an interval of several hours.
The ratio of polyamine of the formula B4a to cyanuric chloride to 2,2,6,6-tetramethyl-4-piperidylamine of the formula B4b is preferably from 1:3:5 to 1:3:6.